CA2060512C - Fireproofing covering material - Google Patents
Fireproofing covering materialInfo
- Publication number
- CA2060512C CA2060512C CA002060512A CA2060512A CA2060512C CA 2060512 C CA2060512 C CA 2060512C CA 002060512 A CA002060512 A CA 002060512A CA 2060512 A CA2060512 A CA 2060512A CA 2060512 C CA2060512 C CA 2060512C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- fireproofing
- covering material
- cement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000004079 fireproofing Methods 0.000 title claims description 75
- 239000000919 ceramic Substances 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 20
- 239000004571 lime Substances 0.000 claims abstract description 20
- 239000004568 cement Substances 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000000057 synthetic resin Substances 0.000 claims abstract description 10
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 10
- 239000011505 plaster Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052602 gypsum Inorganic materials 0.000 abstract 2
- 239000010440 gypsum Substances 0.000 abstract 2
- 230000009970 fire resistant effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000011435 rock Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000012784 inorganic fiber Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Building Environments (AREA)
- Paints Or Removers (AREA)
- Fireproofing Substances (AREA)
- Insulated Conductors (AREA)
Abstract
A refractory coating material comprising cement as the matrix, which is significantly improved in fire resistance or both of fire resistance and durability. The first invention relates to a mixture of 100 parts by weight of cement with 5 to 35 parts by weight of lime, 5 to 35 parts by weight of gypsum, and 5 to 35 parts by weight of aluminosilicate gel, while the second invention relates to a mixture of 100 parts by weight of powdery material, prepared by mixing 100 parts by weight of cement with 5 to 35 parts by weight of lime, 5 to 35 parts by weight of gypsum and 5 to 35 parts by weight of aluminosilicate gel, with 50 to 300 parts by weight of ceramic balloon, 10 to 40 parts by weight of ceramic fiber, and 5 to 20 parts by weight in terms of solid content of synthetic resin emulsion.
Description
FIREPROOFING COVERING MATERIAL
Background of the Invention Field of the Invention - This invention relates to a fireproofing covering material with cement matrix.
Prior Art Buildings are generally required to have certain fire resistant performances for their different parts under the Construction Standard Law.
--- Conventionally, structuring materials such as steel - frames and folded plate ceiling are coated with fireproofing covering materials for improvement of their fire resistant performance.
Such fireproofing covering materials are often mixture of rock fiber and cement because of low cost.
This fireproofing covering material consisting of mixture of rock fiber and cement is sprayed to the surface of the structure when used.
The fireproofing layer formed on the structure by the use of such fireproofing covering material, however, does - not have sufficient durability. It has only a low strength and high water absorption and high moisture permeation coefficient, resulting in weak adhesion.
In other words, when rock fiber fireproofing covering material is sprayed to a structure such as steel frame and folded plate ceiling, for example, a fireproofing layer is formed on the surface of the structure, but this fireproofing layer is susceptible to separation and peeling off due to internal dewing and water absorption.
Such rock fiber fireproofing covering material is accepted by the Standards for fire resistance, but a higher fire resistant performance is required now.
Summary of the invention This invention is made to solve the above mentioned problems. It is an object of the fireproofing covering material of Claim 1 to provide a fireproofing covering material with a largely improved fire resistant performance, and an object of the fireproofing covering material of Claim 2 is to provide a fireproofing covering material with largely improved fire resistant performance and durability.
The fireproofing covering material of Claim 1 comprises 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel.
This fireproofing covering material is, for example, mixed with rock fiber and hydrated and sprayed to structures such as steel frames and folded plate ceiling.
On the fireproofing layer formed on the structure surface, hydration of lime, plaster and aluminosilica gel generate calcium sulfoaluminate-based hydrate product including a large amount of water such as 24H20 and 32H20. Such hydrate products serve for heat reduction when heated.
Lime, plaster and aluminosilica gel themselves have water molecules in their molecular structures and serve for heat reduction effect when the fireproofing layer is heated.
The fireproofing covering material of Claim 2 is prepared by mixing 100 parts by weight of powder (consisting of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel) with 50 to 300 parts by weight of ceramic balloon, 10 to 40 parts by weight of ceramic fiber and 5 to 20 parts by weight (solid content equivalency) of synthetic resin emulsion.
The fireproofing covering material may be applied to the structure by wet or dry process.
Application to structure by wet process is performed by spraying the material in viscous fluid state to a structure such as steel frame or folded plate ceiling or by applying it to structure with a trowel.
Application to structure by dry process is performed, for example, by curing a fireproofing covering material in viscous fluid state to form a plate to be fixed with a jig or adhered with adhesive.
This fireproofing covering material largely improves the fire resistant performance of coating materials for steel frames and other structural materials because of heat reduction effect caused by hydrate product with high water inclusion generated by reaction of lime, plaster and aluminosilica gel when heated and individual heat reduction effect of each of lime, plaster and aluminosilica gel as mentioned above.
Further, this fireproofing covering material contains ceramic balloon and ceramic fiber and a large amount of other inorganic materials, resulting in improving not only fire resistant performance but also insulation performance.
Since the fireproofing covering material contains ceramic fiber and synthetic resin emulsion, ceramic fiber serves as the reinforcement material for a fireproofing 20~0~12 layer formed on the structure surface and makes the internal bonding within the fireproofing covering material strong and effectively prevents cracks at the time of application to structure or heating. Further, synthetic resin emulsion improves adhesion to the structure and prevents the material from being separated when it is adhered to the structure or when heated.
In addition, when compared to conventional fireproofing coverinq materials, the fireproofing covering material of this invention has a more solid matrix and contains the ceramic balloon in complete closed-cell state.
This resuLts in a lower water absorption and moisture permeation coefficients and prevents the dewing within the fireproofing layer from occurring.
This material also improves the strength and adhesion of fireproofing layer and reduces the moisture permeability and mixing of ceramic balloon makes the material weight lighter. In addition, this fireproofing covering material is much stronger than conventional ones and can be finished with a smooth surface, and the fireproofing layer itself can be used as the finish surface or can be used as the base for direct finishing such as painting, spraying, clothing and tiling.
In particular, when a small amount of ceramic balloon is mixed, the surface of the fireproofing layer becomes smooth and can be used as the finishing layer.
In this invention, lime, plaster and aluminosilica gel are respectively added by 5 to 35 parts by weight to 100 parts by weight of cement. If they are below 5 parts by weight, heat generation suppressing effect when the fireproofing covering material is heated will be too small i- 2060SI2 and if they are more than 35 parts by weight, the fireproofing layer formed on the structure will become weaker.
To 100 parts by weight of powder, ceramic balloon is added by 50 to 300 parts by weight because sufficient lightness and heat insulation performance cannot be expected by addition of ceramic balloon below 50 parts by ~eight and the strength will be lower when ceramic balloon becomes more than 300 parts by weight. The best amount of ceramic balloon which will bring a high strength and good finish is about 50 parts by weight.
- Furt~er, to 100 parts by weight of powder, synthetic resin emulsion is added by 5 to 20 parts by weight (solid content equivalency) because the adhesion is not sufficient when it is less than 5 parts by weight and the fire resistant performance will be degraded when it is more than 20 parts by weight.
To 100 parts by weight of powder, ceramic fiber is added by 10 to 40 pàrts by weight because the ceramic fiber less than 10 parts by weight cannot realize sufficient reinforcement effect and that more than 40 parts by weight makes the cement brittle by reducing the bonding power - (binder effect) of the cement to be a matrix.
Brief Description of the Drawings Fig. 1 is a graph showing the results of fire resistance test of a fireproofing plate formed by curing the fireproofing covering material of this invention.
Fig. 2 is an explanatory view illustrating the positions to take temperature data for fireproofing plate in fire resistance test.
~ 20~0512 Description of the Preferred Embodiments Preferred embodiments of this invention are described below.
Embodiment To obtain a fireproofing covering material of this invention, powder is prepared by mixing 100 parts by weight of high-early-strength Portland cement, 14.3 parts by weight of lime, 14.3 parts by weight of plaster and 14.3 parts by weight of aluminosilica gel.
To 100 parts by weight of the powder obtained are added 200 parts by weight of ceramic balloon, 33.3 parts by weight of ceramic fiber, 15 parts by weight of ethylene-vinyl acetate based emulsion (solid content density: 9%) in solid content equivalency and a small amount of thickening agent and antifoamer, all of which are mixed and kneaded.
Aluminosilica gel is, for example, volcanic ash such as allophane.
Ceramic fiber has, for example, a fiber length of about 6 mm.
Ceramic balloon haæ a particle diameter of 5 to 200 micrometers for example and a specific gravity of 0.3 to 0.7.
Thickening agent is a water soluble high molecular compound such as methyl cellulose, polyvinyl alcohol and hydroxyethyl cellulose.
When the fireproofing covering material thus formed was cured and tested for its performance, it had a bending strength of 14.4 kgf/cm2, a compressive strength of 30.1 kgf/cm2, and a specific gravity of 0.55.
.
Embodiment 2 To 100 parts by weight of high-early-strength Portland cement are mixed 27.3 parts by weight of lime, 27.3 parts by weight of plaster and 27.3 parts by weight of aluminosilica gel to prepare powder.
To 100 parts by weight of this powder are added 100 parts by weight of ceramic balloon, 16.7 parts by weight of ceramic fiber and 7.5 parts by weight (in solid content equivalency) of ethylene-vinyl acetate based emulsion (solid content density: 9%) and a small amount of water-soluble resin and the mixture is mixed and kneaded.
When the fireproofing covering material thus formed was cured and subjected to performance test, it had a bending strength of 23.3 kgf/cm2, a compressive strength of 62.4 kgf/cm2, and a specific gravity of 0.65.
For this embodiment 2, heating test was effected according to JIS-A-1304 "Method of Fire Resistance Test for Structural Parts of Buildings". Fig. 1 shows the test results.
In this figure, ordinate axis indicates temperature(C) and abscissa axis indicates the time elapsed (minutes).
The solid line indicates the heating temperature; the dot and dash line indicates the temperature at the point 20 mm apart from the heated surface of the fireproofing plate, made by curing of the fireproofing covering material of this invention, that is the internal temperature at point A
of the fireproofing covering material plate shown in Fig.
Background of the Invention Field of the Invention - This invention relates to a fireproofing covering material with cement matrix.
Prior Art Buildings are generally required to have certain fire resistant performances for their different parts under the Construction Standard Law.
--- Conventionally, structuring materials such as steel - frames and folded plate ceiling are coated with fireproofing covering materials for improvement of their fire resistant performance.
Such fireproofing covering materials are often mixture of rock fiber and cement because of low cost.
This fireproofing covering material consisting of mixture of rock fiber and cement is sprayed to the surface of the structure when used.
The fireproofing layer formed on the structure by the use of such fireproofing covering material, however, does - not have sufficient durability. It has only a low strength and high water absorption and high moisture permeation coefficient, resulting in weak adhesion.
In other words, when rock fiber fireproofing covering material is sprayed to a structure such as steel frame and folded plate ceiling, for example, a fireproofing layer is formed on the surface of the structure, but this fireproofing layer is susceptible to separation and peeling off due to internal dewing and water absorption.
Such rock fiber fireproofing covering material is accepted by the Standards for fire resistance, but a higher fire resistant performance is required now.
Summary of the invention This invention is made to solve the above mentioned problems. It is an object of the fireproofing covering material of Claim 1 to provide a fireproofing covering material with a largely improved fire resistant performance, and an object of the fireproofing covering material of Claim 2 is to provide a fireproofing covering material with largely improved fire resistant performance and durability.
The fireproofing covering material of Claim 1 comprises 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel.
This fireproofing covering material is, for example, mixed with rock fiber and hydrated and sprayed to structures such as steel frames and folded plate ceiling.
On the fireproofing layer formed on the structure surface, hydration of lime, plaster and aluminosilica gel generate calcium sulfoaluminate-based hydrate product including a large amount of water such as 24H20 and 32H20. Such hydrate products serve for heat reduction when heated.
Lime, plaster and aluminosilica gel themselves have water molecules in their molecular structures and serve for heat reduction effect when the fireproofing layer is heated.
The fireproofing covering material of Claim 2 is prepared by mixing 100 parts by weight of powder (consisting of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel) with 50 to 300 parts by weight of ceramic balloon, 10 to 40 parts by weight of ceramic fiber and 5 to 20 parts by weight (solid content equivalency) of synthetic resin emulsion.
The fireproofing covering material may be applied to the structure by wet or dry process.
Application to structure by wet process is performed by spraying the material in viscous fluid state to a structure such as steel frame or folded plate ceiling or by applying it to structure with a trowel.
Application to structure by dry process is performed, for example, by curing a fireproofing covering material in viscous fluid state to form a plate to be fixed with a jig or adhered with adhesive.
This fireproofing covering material largely improves the fire resistant performance of coating materials for steel frames and other structural materials because of heat reduction effect caused by hydrate product with high water inclusion generated by reaction of lime, plaster and aluminosilica gel when heated and individual heat reduction effect of each of lime, plaster and aluminosilica gel as mentioned above.
Further, this fireproofing covering material contains ceramic balloon and ceramic fiber and a large amount of other inorganic materials, resulting in improving not only fire resistant performance but also insulation performance.
Since the fireproofing covering material contains ceramic fiber and synthetic resin emulsion, ceramic fiber serves as the reinforcement material for a fireproofing 20~0~12 layer formed on the structure surface and makes the internal bonding within the fireproofing covering material strong and effectively prevents cracks at the time of application to structure or heating. Further, synthetic resin emulsion improves adhesion to the structure and prevents the material from being separated when it is adhered to the structure or when heated.
In addition, when compared to conventional fireproofing coverinq materials, the fireproofing covering material of this invention has a more solid matrix and contains the ceramic balloon in complete closed-cell state.
This resuLts in a lower water absorption and moisture permeation coefficients and prevents the dewing within the fireproofing layer from occurring.
This material also improves the strength and adhesion of fireproofing layer and reduces the moisture permeability and mixing of ceramic balloon makes the material weight lighter. In addition, this fireproofing covering material is much stronger than conventional ones and can be finished with a smooth surface, and the fireproofing layer itself can be used as the finish surface or can be used as the base for direct finishing such as painting, spraying, clothing and tiling.
In particular, when a small amount of ceramic balloon is mixed, the surface of the fireproofing layer becomes smooth and can be used as the finishing layer.
In this invention, lime, plaster and aluminosilica gel are respectively added by 5 to 35 parts by weight to 100 parts by weight of cement. If they are below 5 parts by weight, heat generation suppressing effect when the fireproofing covering material is heated will be too small i- 2060SI2 and if they are more than 35 parts by weight, the fireproofing layer formed on the structure will become weaker.
To 100 parts by weight of powder, ceramic balloon is added by 50 to 300 parts by weight because sufficient lightness and heat insulation performance cannot be expected by addition of ceramic balloon below 50 parts by ~eight and the strength will be lower when ceramic balloon becomes more than 300 parts by weight. The best amount of ceramic balloon which will bring a high strength and good finish is about 50 parts by weight.
- Furt~er, to 100 parts by weight of powder, synthetic resin emulsion is added by 5 to 20 parts by weight (solid content equivalency) because the adhesion is not sufficient when it is less than 5 parts by weight and the fire resistant performance will be degraded when it is more than 20 parts by weight.
To 100 parts by weight of powder, ceramic fiber is added by 10 to 40 pàrts by weight because the ceramic fiber less than 10 parts by weight cannot realize sufficient reinforcement effect and that more than 40 parts by weight makes the cement brittle by reducing the bonding power - (binder effect) of the cement to be a matrix.
Brief Description of the Drawings Fig. 1 is a graph showing the results of fire resistance test of a fireproofing plate formed by curing the fireproofing covering material of this invention.
Fig. 2 is an explanatory view illustrating the positions to take temperature data for fireproofing plate in fire resistance test.
~ 20~0512 Description of the Preferred Embodiments Preferred embodiments of this invention are described below.
Embodiment To obtain a fireproofing covering material of this invention, powder is prepared by mixing 100 parts by weight of high-early-strength Portland cement, 14.3 parts by weight of lime, 14.3 parts by weight of plaster and 14.3 parts by weight of aluminosilica gel.
To 100 parts by weight of the powder obtained are added 200 parts by weight of ceramic balloon, 33.3 parts by weight of ceramic fiber, 15 parts by weight of ethylene-vinyl acetate based emulsion (solid content density: 9%) in solid content equivalency and a small amount of thickening agent and antifoamer, all of which are mixed and kneaded.
Aluminosilica gel is, for example, volcanic ash such as allophane.
Ceramic fiber has, for example, a fiber length of about 6 mm.
Ceramic balloon haæ a particle diameter of 5 to 200 micrometers for example and a specific gravity of 0.3 to 0.7.
Thickening agent is a water soluble high molecular compound such as methyl cellulose, polyvinyl alcohol and hydroxyethyl cellulose.
When the fireproofing covering material thus formed was cured and tested for its performance, it had a bending strength of 14.4 kgf/cm2, a compressive strength of 30.1 kgf/cm2, and a specific gravity of 0.55.
.
Embodiment 2 To 100 parts by weight of high-early-strength Portland cement are mixed 27.3 parts by weight of lime, 27.3 parts by weight of plaster and 27.3 parts by weight of aluminosilica gel to prepare powder.
To 100 parts by weight of this powder are added 100 parts by weight of ceramic balloon, 16.7 parts by weight of ceramic fiber and 7.5 parts by weight (in solid content equivalency) of ethylene-vinyl acetate based emulsion (solid content density: 9%) and a small amount of water-soluble resin and the mixture is mixed and kneaded.
When the fireproofing covering material thus formed was cured and subjected to performance test, it had a bending strength of 23.3 kgf/cm2, a compressive strength of 62.4 kgf/cm2, and a specific gravity of 0.65.
For this embodiment 2, heating test was effected according to JIS-A-1304 "Method of Fire Resistance Test for Structural Parts of Buildings". Fig. 1 shows the test results.
In this figure, ordinate axis indicates temperature(C) and abscissa axis indicates the time elapsed (minutes).
The solid line indicates the heating temperature; the dot and dash line indicates the temperature at the point 20 mm apart from the heated surface of the fireproofing plate, made by curing of the fireproofing covering material of this invention, that is the internal temperature at point A
of the fireproofing covering material plate shown in Fig.
2: the two-dot and dash line indicates the temperature at the point 30 mm apart from the heated surface of the fireproofing plate 11, that is the internal temperature at point B of the fireproofing plate 11 shown in Fig. 2; and the broken line indicates the internal temperature at the point 20 mm apart from the heated surface of a conventional (approved by the Ministry of Construction) inorganic fiber mixed calcium silicate plate (No. 1).
The inorganic fiber mixed calcium silicate plate as a conventional product has a specific gravity of 0.4 or more, a bending strength of 25 kgf/cm2, and a compressive strength of 30 kgf/cm2.
The fireproofing plate 11 is 40 mm thick and 500 mm wide and 500 mm long. This fireproofing plate 11 is horizontally placed on the top of the heating device (300 mm wide and deep and 500 mm high. Combustion: municipal gas) and heated for at least one hour.
As a result, as shown in Fig. 1, the fireproofing plate 11 provided with the cured fireproofing covering material of this invention shows a temperature below the allowable steel material temperature (450 C at most and 350 C on average) when 60 minutes have elapsed. Inorganic fiber mixed calcium silicate plate shows a temperature below the maximum allowable steel material temperature (450 C) but over the average allowable steel material temperature (350 C) when 60 minutes have passed.
The temperature at the point 30 mm apart from the heated surface of the fireproofing plate 11, i.e. the internal temperature at point B is below 260 C, which is the allowable backside temperature for partition walls when 60 minutes have passed.
When compared with a conventional inorganic fiber mixed calcium silicate plate, internal temperature rises gently and the time elapsed until the maximum allowable steel material temperature of 450 C, average allowable steel material temperature of 350 C, or allowable backside temperature of 260 C are reached is greatly extended.
This means that the fireproofing plate 11 using the fireproofing covering material of this invention has the better fire resistant performance.
When the internal temperatures are compared between the points A and B of the fireproofing plate 11, the point B shows extremely slower rising of the internal temperature than the point A. This tells that the thicker the fireproofing covering material of this invention becomes, the better the fire resistant performance improves.
Even when the amounts of the ingredients to 100 parts by weight of cement are changed in the range of 5 to 35 parts by weight for lime, 5 to 35 parts by weight for plaster and 5 to 35 parts by weight for aluminosilica gel, almost the same effect as the above embodiment can be obtained.
To 100 parts by weight of the powder formed by mixing 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster, and 5 to 35 parts by weight of aluminosilica gel with 100 parts by weight of cement, amount of the ingredients may be changed in the range of 50 to 300 parts by weight for ceramic balloon, 10 to 40 parts by weight for ceramic fiber, and 5 to 20 parts by weight (solid content equivalency) for synthetic resin emulsion to obtain the similar effect as the above embodiment. By changing the ratio of the ingredients, strength and finishing states can be changed, so that a fireproofing covering material having the fire-resistant performance, strength and finish suitable for its application can be obtained.
.
g Although the invention has been described in its preferred embodiments where a small amount of thic]cening agent and antifoamer are added, it is understood that the invention is not limited to these specific embodiments, and almost the same effect as the above embodiments can be obtained without adding such thickening agent and antifoamer or with adding other materials as necessary.
Industrial Applicability The fireproofing covering material of Claim 1 consisting of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 3s parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel can largely improve the fire resistant performance.
Such a fireproofing covering material may be, for example, hydrated by mixing with rock fiber as in conventional procedures and sprayed to the structure.
The fireproofing layer formed on the structure surface causes calcium-sulfo-aluminate based hydrated products containing much amount of water such as 24H20 and 32H20 to be generated by hydration reaction among lime, plaster and aluminosilica gel, these hydrated products serving for heat reduction when the material is heated and lime, plaster and , .
aluminosilica gel themselves having some water molecules in their molecular structure also serve for heat reduction when the fireproofing layer is heated and largely improve the fire resistant performance of the coated material such as steel frame.
The fireproofing covering material of Claim 2 is made of 100 parts by weight of powder which consists of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel and to which 50 to 300 parts by weight of ceramic balloon, 10 to 40 parts by weight of ceramic fiber and 5 to 20 parts by weight (solid content equivalency) of synthetic resin emulsion are added and can largely improve the fire resistant performance and durability.
Addition of lime, plaster and aluminosilicagel considerably improves the fire resistant performance of the coated material such as steel frames because of the heat generation suppressing effect against heating of the hydrated product generated by hydrate reaction and heat generation suppressing effect of each ingredient. In addition, mixing of ceramic balloon and ceramic fiber results in that high amount of inorganic material contents, which improves fire resistant performance and heat insulation performance.
Further, containing of ceramic fiber and synthetic resin emulsion causes the ceramic fiber to serve as the reinforcing material and enhance the internal bonding of the fireproofing covering material, which effectively prevents cracks to be generated at the time of adhesion to the structure or of heating. The synthetic resin emulsion also improves adhesion to the structure and ensures to prevent the material from being separated during adhesion and when heated.
Compared to conventional fireproofing covering material, matrix of this material is more solid and the ceramic balloon to be mixed to is in complete closed-cell state. This makes the water absorption and moisture permeation coefficient smaller, which prevents internal dewing in the fireproofing layer and ensures to prevent the separation of the fireproofing layer.
The fireproofing covering materia] of this invention has a compressive strength of 30 to 70 kfg/cm2, a tensile strength of 10 kgf/cm2 or more and a water absorption ratio of around 20 to 30~.
In contrast, rock fiber fireproofing covering material generally used has a larger amount of rock fiber compared to the amount of cement which causes binder effect in its material ingredients, it is quite dry and both compressive strength and tensile strength are 1 kgf/cm2 or less and the - water absorption ration is so high that the water can be absorbed until saturation. Moisture permeation resistance is also quite poor.
Thus, the fireproofing covering material of this invention can improve the strength and adhesion of the fireproofing layer and reduce the moisture permeation coefficient. In addition, mixing of ceramic balloon contributes to a lighter weight. Accordingly, the fireproofing layer itself can be used as finish surface, or can be used as the base for direct painting, spraying, clothing or tiling.
-- In particular, mixing of ceramic balloon in a small amount causes the fireproofing layer surface to be quite smooth and can be used as the finish surface as it is.
The inorganic fiber mixed calcium silicate plate as a conventional product has a specific gravity of 0.4 or more, a bending strength of 25 kgf/cm2, and a compressive strength of 30 kgf/cm2.
The fireproofing plate 11 is 40 mm thick and 500 mm wide and 500 mm long. This fireproofing plate 11 is horizontally placed on the top of the heating device (300 mm wide and deep and 500 mm high. Combustion: municipal gas) and heated for at least one hour.
As a result, as shown in Fig. 1, the fireproofing plate 11 provided with the cured fireproofing covering material of this invention shows a temperature below the allowable steel material temperature (450 C at most and 350 C on average) when 60 minutes have elapsed. Inorganic fiber mixed calcium silicate plate shows a temperature below the maximum allowable steel material temperature (450 C) but over the average allowable steel material temperature (350 C) when 60 minutes have passed.
The temperature at the point 30 mm apart from the heated surface of the fireproofing plate 11, i.e. the internal temperature at point B is below 260 C, which is the allowable backside temperature for partition walls when 60 minutes have passed.
When compared with a conventional inorganic fiber mixed calcium silicate plate, internal temperature rises gently and the time elapsed until the maximum allowable steel material temperature of 450 C, average allowable steel material temperature of 350 C, or allowable backside temperature of 260 C are reached is greatly extended.
This means that the fireproofing plate 11 using the fireproofing covering material of this invention has the better fire resistant performance.
When the internal temperatures are compared between the points A and B of the fireproofing plate 11, the point B shows extremely slower rising of the internal temperature than the point A. This tells that the thicker the fireproofing covering material of this invention becomes, the better the fire resistant performance improves.
Even when the amounts of the ingredients to 100 parts by weight of cement are changed in the range of 5 to 35 parts by weight for lime, 5 to 35 parts by weight for plaster and 5 to 35 parts by weight for aluminosilica gel, almost the same effect as the above embodiment can be obtained.
To 100 parts by weight of the powder formed by mixing 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster, and 5 to 35 parts by weight of aluminosilica gel with 100 parts by weight of cement, amount of the ingredients may be changed in the range of 50 to 300 parts by weight for ceramic balloon, 10 to 40 parts by weight for ceramic fiber, and 5 to 20 parts by weight (solid content equivalency) for synthetic resin emulsion to obtain the similar effect as the above embodiment. By changing the ratio of the ingredients, strength and finishing states can be changed, so that a fireproofing covering material having the fire-resistant performance, strength and finish suitable for its application can be obtained.
.
g Although the invention has been described in its preferred embodiments where a small amount of thic]cening agent and antifoamer are added, it is understood that the invention is not limited to these specific embodiments, and almost the same effect as the above embodiments can be obtained without adding such thickening agent and antifoamer or with adding other materials as necessary.
Industrial Applicability The fireproofing covering material of Claim 1 consisting of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 3s parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel can largely improve the fire resistant performance.
Such a fireproofing covering material may be, for example, hydrated by mixing with rock fiber as in conventional procedures and sprayed to the structure.
The fireproofing layer formed on the structure surface causes calcium-sulfo-aluminate based hydrated products containing much amount of water such as 24H20 and 32H20 to be generated by hydration reaction among lime, plaster and aluminosilica gel, these hydrated products serving for heat reduction when the material is heated and lime, plaster and , .
aluminosilica gel themselves having some water molecules in their molecular structure also serve for heat reduction when the fireproofing layer is heated and largely improve the fire resistant performance of the coated material such as steel frame.
The fireproofing covering material of Claim 2 is made of 100 parts by weight of powder which consists of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel and to which 50 to 300 parts by weight of ceramic balloon, 10 to 40 parts by weight of ceramic fiber and 5 to 20 parts by weight (solid content equivalency) of synthetic resin emulsion are added and can largely improve the fire resistant performance and durability.
Addition of lime, plaster and aluminosilicagel considerably improves the fire resistant performance of the coated material such as steel frames because of the heat generation suppressing effect against heating of the hydrated product generated by hydrate reaction and heat generation suppressing effect of each ingredient. In addition, mixing of ceramic balloon and ceramic fiber results in that high amount of inorganic material contents, which improves fire resistant performance and heat insulation performance.
Further, containing of ceramic fiber and synthetic resin emulsion causes the ceramic fiber to serve as the reinforcing material and enhance the internal bonding of the fireproofing covering material, which effectively prevents cracks to be generated at the time of adhesion to the structure or of heating. The synthetic resin emulsion also improves adhesion to the structure and ensures to prevent the material from being separated during adhesion and when heated.
Compared to conventional fireproofing covering material, matrix of this material is more solid and the ceramic balloon to be mixed to is in complete closed-cell state. This makes the water absorption and moisture permeation coefficient smaller, which prevents internal dewing in the fireproofing layer and ensures to prevent the separation of the fireproofing layer.
The fireproofing covering materia] of this invention has a compressive strength of 30 to 70 kfg/cm2, a tensile strength of 10 kgf/cm2 or more and a water absorption ratio of around 20 to 30~.
In contrast, rock fiber fireproofing covering material generally used has a larger amount of rock fiber compared to the amount of cement which causes binder effect in its material ingredients, it is quite dry and both compressive strength and tensile strength are 1 kgf/cm2 or less and the - water absorption ration is so high that the water can be absorbed until saturation. Moisture permeation resistance is also quite poor.
Thus, the fireproofing covering material of this invention can improve the strength and adhesion of the fireproofing layer and reduce the moisture permeation coefficient. In addition, mixing of ceramic balloon contributes to a lighter weight. Accordingly, the fireproofing layer itself can be used as finish surface, or can be used as the base for direct painting, spraying, clothing or tiling.
-- In particular, mixing of ceramic balloon in a small amount causes the fireproofing layer surface to be quite smooth and can be used as the finish surface as it is.
Claims (2)
1. A fireproofing covering material consisting of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel.
2. A fireproofing covering material comprising 100 parts by weight of powder consisting of 100 parts by weight of cement, 5 to 35 parts by weight of lime, 5 to 35 parts by weight of plaster and 5 to 35 parts by weight of aluminosilica gel, 50 to 300 parts by weight of ceramic balloon, 10 to 40 parts by weight by ceramic fiber and 5 to 20 parts by weight (solid content equivalency) of synthetic resin emulsion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2109548A JP2829093B2 (en) | 1990-04-25 | 1990-04-25 | Fireproof coating |
JP2-109548 | 1990-04-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2060512A1 CA2060512A1 (en) | 1991-10-26 |
CA2060512C true CA2060512C (en) | 1996-08-13 |
Family
ID=14513040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002060512A Expired - Fee Related CA2060512C (en) | 1990-04-25 | 1991-04-24 | Fireproofing covering material |
Country Status (11)
Country | Link |
---|---|
US (1) | US5259872A (en) |
EP (1) | EP0480072B1 (en) |
JP (1) | JP2829093B2 (en) |
KR (1) | KR950002916B1 (en) |
CN (1) | CN1048235C (en) |
CA (1) | CA2060512C (en) |
DE (1) | DE69111015T2 (en) |
FI (1) | FI97724C (en) |
NO (1) | NO302881B1 (en) |
SE (1) | SE470165B (en) |
WO (1) | WO1991016275A1 (en) |
Families Citing this family (22)
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JP3988843B2 (en) * | 1997-03-24 | 2007-10-10 | 株式会社エーアンドエーマテリアル | Wet spray fireproof coating composition |
PL358677A1 (en) | 2000-03-14 | 2004-08-09 | James Hardie Research Pty Limited | Fiber cement building materials with low density additives |
BR0208621A (en) | 2001-04-03 | 2004-04-27 | James Hardie Res Pty Ltd | Fiber-cement external wall boards, their production processes and installation |
KR100525564B1 (en) * | 2002-05-03 | 2005-10-31 | 주식회사 경동세라텍 | Covering composite for fire resistance and sound absorption |
US8281535B2 (en) | 2002-07-16 | 2012-10-09 | James Hardie Technology Limited | Packaging prefinished fiber cement articles |
US8297018B2 (en) | 2002-07-16 | 2012-10-30 | James Hardie Technology Limited | Packaging prefinished fiber cement products |
MXPA05003691A (en) | 2002-10-07 | 2005-11-17 | James Hardie Int Finance Bv | Durable medium-density fibre cement composite. |
US8132382B2 (en) | 2004-06-17 | 2012-03-13 | Certainteed Corporation | Insulation containing heat expandable spherical additives, calcium acetate, cupric carbonate, or a combination thereof |
US20050281979A1 (en) * | 2004-06-17 | 2005-12-22 | Toas Murray S | Loose fill insulation product having phase change material therein |
US7998571B2 (en) | 2004-07-09 | 2011-08-16 | James Hardie Technology Limited | Composite cement article incorporating a powder coating and methods of making same |
KR100609989B1 (en) * | 2004-12-08 | 2006-08-08 | 제일모직주식회사 | Artificial marble composition with both Hanji pattern and subtle texture |
CN1300062C (en) * | 2005-10-14 | 2007-02-14 | 宜兴天霸非金属材料有限公司 | Setting accelerated fibre fire-proof plastic and production thereof |
MX2008013202A (en) | 2006-04-12 | 2009-01-09 | James Hardie Int Finance Bv | A surface sealed reinforced building element. |
US7726086B2 (en) * | 2007-02-05 | 2010-06-01 | Certainteed Corporation | Panel of roofing shingles |
US8209927B2 (en) | 2007-12-20 | 2012-07-03 | James Hardie Technology Limited | Structural fiber cement building materials |
CN101671197B (en) * | 2009-09-23 | 2012-11-21 | 北京航空航天大学 | Preparation method of carbon foam heat insulation material added with hollow ceramic balls |
JP5692579B2 (en) | 2010-02-12 | 2015-04-01 | 株式会社リコー | Toner manufacturing method, toner, image forming method using the same, and process cartridge |
JP6212982B2 (en) * | 2013-06-27 | 2017-10-18 | 宇部興産株式会社 | Heat-resistant hydraulic composition, mortar composition, and mortar cured body used for ship floor structures |
CN103641496B (en) * | 2013-11-26 | 2015-02-11 | 江苏博思源防火材料科技有限公司 | Expansive type tunnel fireproof paint |
JP6416005B2 (en) * | 2015-02-06 | 2018-10-31 | 株式会社熊谷組 | Method for forming fireproof paint layer |
KR101684920B1 (en) * | 2016-02-29 | 2016-12-09 | 장재일 | Non-Shrink Grout Material Composition |
CN114044664B (en) * | 2021-12-15 | 2022-09-30 | 河北嘉固新材料科技有限公司 | Anti-freezing and salt-freezing-resistant rapid repairing material for cement pavement of airport and preparation method thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2526014A1 (en) * | 1982-05-03 | 1983-11-04 | Chollet Jacques | Fire-resistant and thermally insulating coating or mortar - contains plaster, Portland cement, calcite, rhyolite, and lightweight expanded inorganic or polymer aggregate |
JPS598659A (en) * | 1982-07-07 | 1984-01-17 | 藤井 実 | Lightweight body composition |
DE3230406A1 (en) * | 1982-08-16 | 1984-02-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München | BINDER MIXTURE OF SULFATIC, LIME-DISPENSING AND PUZZOLANIC SUBSTANCES |
JPS59128248A (en) * | 1983-01-12 | 1984-07-24 | 宇部興産株式会社 | Super low gravity cement and cement slurry for high temperature |
JP2538588B2 (en) * | 1987-04-03 | 1996-09-25 | 三井石油化学工業株式会社 | Method for producing solid catalyst for olefin polymerization |
CN1012740B (en) * | 1987-07-10 | 1991-06-05 | 唐山水泥机械厂 | Medium alloy modified wear-resistant cast steel |
JPH085733B2 (en) * | 1987-12-16 | 1996-01-24 | 株式会社竹中工務店 | Inorganic heat insulating material |
JPH01308856A (en) * | 1988-06-07 | 1989-12-13 | Yoshizawa Sekkai Kogyo Kk | Filler composition |
-
1990
- 1990-04-25 JP JP2109548A patent/JP2829093B2/en not_active Expired - Fee Related
-
1991
- 1991-04-24 CA CA002060512A patent/CA2060512C/en not_active Expired - Fee Related
- 1991-04-24 KR KR1019910701532A patent/KR950002916B1/en not_active IP Right Cessation
- 1991-04-24 US US07/778,227 patent/US5259872A/en not_active Expired - Lifetime
- 1991-04-24 WO PCT/JP1991/000550 patent/WO1991016275A1/en active IP Right Grant
- 1991-04-24 DE DE69111015T patent/DE69111015T2/en not_active Expired - Fee Related
- 1991-04-24 CN CN91103427A patent/CN1048235C/en not_active Expired - Fee Related
- 1991-04-24 EP EP91908795A patent/EP0480072B1/en not_active Expired - Lifetime
- 1991-10-23 SE SE9103101A patent/SE470165B/en not_active IP Right Cessation
- 1991-12-11 NO NO914879A patent/NO302881B1/en unknown
- 1991-12-20 FI FI916082A patent/FI97724C/en active
Also Published As
Publication number | Publication date |
---|---|
SE9103101L (en) | 1993-04-24 |
SE470165B (en) | 1993-11-22 |
KR920701068A (en) | 1992-08-11 |
EP0480072B1 (en) | 1995-07-05 |
CA2060512A1 (en) | 1991-10-26 |
DE69111015D1 (en) | 1995-08-10 |
JP2829093B2 (en) | 1998-11-25 |
EP0480072A4 (en) | 1993-01-27 |
KR950002916B1 (en) | 1995-03-28 |
DE69111015T2 (en) | 1995-11-02 |
FI916082A0 (en) | 1991-12-20 |
WO1991016275A1 (en) | 1991-10-31 |
NO914879L (en) | 1991-12-11 |
CN1048235C (en) | 2000-01-12 |
NO302881B1 (en) | 1998-05-04 |
EP0480072A1 (en) | 1992-04-15 |
NO914879D0 (en) | 1991-12-11 |
CN1057448A (en) | 1992-01-01 |
FI97724C (en) | 1997-02-10 |
FI97724B (en) | 1996-10-31 |
JPH046136A (en) | 1992-01-10 |
US5259872A (en) | 1993-11-09 |
SE9103101D0 (en) | 1991-10-23 |
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